A Ni(II)-catalyzed asymmetric difunctionalization of alkynes is reported. This method involves intermolecular regioselective arylation of the alkynes and intramolecular desymmetrization of dinitriles, enabling the synthesis of enantioenriched azepine derivatives. The reaction exhibits good tolerance toward various functional groups, resulting in high yields and enantioselectivities.

Comprehensive Summary

The azepine ring is a prominent structural scaffold in biologically significant molecules. In this study, we present a Ni(II)-catalyzed asymmetric difunctionalization of alkynes, involving intermolecular regioselective arylation and intramolecular nitrile addition, enabling the synthesis of enantioenriched azepine derivatives. This reaction simultaneously installs an all-carbon quaternary stereocenter and introduces an unprotected imine functionality, showing great promise for subsequent transformations. The reaction exhibits good tolerance toward various functional groups, resulting in high yields and enantioselectivities. The synthetic utility of this methodology is further demonstrated through gram-scale synthesis and product derivatization. This research offers an efficient approach to the synthesis of seven-membered nitrogen heterocycles.

2-Aminobenzothiazoles derivatives have revealed a broad spectrum of biological activities, such as anti-HIV, anti-inflammatory, antioxidant, anti-microbial, anti-tumour, anti-infective, and anti-convulsant activities. A great amount of 2-aminobenzothiazole derivatives have been applied in drugs for the treatment of human diseases. A convenient approach for the construction of 2-aminobenzothiazoles via I₂-catalyzed tandem cyclization reaction of amines and carbon disulfide has been developed. More details are discussed in the article by Deng et al. on page 846—852.

2-Aminobenzothiazoles derivatives have revealed a broad spectrum of biological activities, such as anti-HIV, anti-inflammatory, antioxidant, anti-microbial, anti-tumour, anti-infective, and anti-convulsant activities. A great amount of 2-aminobenzothiazole derivatives have been applied in drugs for the treatment of human diseases. A convenient approach for the construction of 2-aminobenzothiazoles via I₂-catalyzed tandem cyclization reaction of amines and carbon disulfide has been developed. More details are discussed in the article by Deng et al. on page 846—852.

An asymmetric hydrosilylation of 2,2-difluoro-1,3-diketones was successfully realized by using a frustrated Lewis pair of chiral borane and tricyclohexylphosphine as a catalyst to give a variety of α,α-difluoro-β-hydroxyketones in high yields with up to 99% ee.

Comprehensive Summary

The asymmetric partial reduction of 1,3-diketones stands as a straightforward pathway to access optically active β-hydroxyketones. In this paper, an asymmetric Piers-type hydrosilylation of 2,2-difluoro-1,3-diketones was successfully realized by using a frustrated Lewis pair of chiral borane and tricyclohexylphosphine as a catalyst, delivering a variety of α,α-difluoro-β-hydroxyketones in high yields with up to 99% ee. Significantly, no over-reduced diol products were observed even with an excess amount of silanes. The product can be conveniently converted to α,α-difluoro-β-hydroxyester or 1,3-anti-diol via an oxidation with m-CPBA or a reduction with DIBAL-H without obvious loss of ee.

A convenient approach for the construction of 2-aminobenzothiazoles via I₂-catalyzed tandem cyclization reaction of amines and carbon disulfide has been developed.

Comprehensive Summary

A convenient approach for the construction of 2-aminobenzothiazoles via I₂-catalyzed tandem cyclization reaction of amines and carbon disulfide has been developed. The present approach starts from simple and readily available starting materials, affording a series of 2-aminobenzothiazoles in up to 89% yields under metal-free conditions. In this work, C—H/N—H functionalization was achieved and multiple C-hetero bonds were successfully constructed in one pot.

It is worth noting that this is the first example of alkoxycarbonyl radical addition to ynones, providing a series of novel functional derivatives. An IrIII-catalyzed cascade radical addition reaction of biaryl ynones to access two classes of carbon rings has been developed. Key to the desired transformations is the regioselective radical addition to different substituted alkyne.

Comprehensive Summary

Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules. Ynones are good regional selectivity radical acceptors in organic synthesis, and many of bio-relevant cyclic compounds could be easily obtained by direct radical cyclization reaction. Here, we report a photocatalytic cascade radical addition of biaryl ynones, for the divergent synthesis of privileged carbon cycles. Additionally, further transformation of the multi-functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.

A synergistic α-glycosylation method with GlcN₃ as donors has been developed, which enjoys mild reaction conditions, good to high yields, and high stereoselectivities. Furthermore, collective syntheses of A. baumannii CPS K43, K47 and K88 repeating units 1—3 have been achieved for the first time via applications of this α-glycosylation method.

Comprehensive Summary

Collective syntheses of A. baumannii CPS K43, K47 and K88 repeating units have been accomplished via a new α-glycosylation method with GlcN₃ as donors, which features: 1) mild reaction conditions, 2) good to high yields, 3) excellent stereoselectivities. The synthetic route also highlights an orthogonal one-pot coupling strategy on the basis of glycosyl ortho-(1-phenylvinyl)benzoates for stereoselective constructions of both 1,2-trans and 1,2-cis glycosidic bonds, precluding the issues of aglycone transfer.

Reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization-induced self-assembly (PISA) mediated by a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is developed, allowing for the synthesis of a diverse set of self-assembled star/linear block copolymer blends.

Comprehensive Summary

Reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization-induced self-assembly (PISA) of star block copolymer and linear block copolymer using a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is reported. With this formulation, star block copolymer and diblock copolymer were formed simultaneously to generate colloidally stable star/linear block copolymer assemblies. Size exclusion chromatography (SEC) analysis confirmed the presence of two types of polymers in the final samples. The molar ratio of the star-like macro-RAFT agent and the linear macro-RAFT agent has a significant impact on the morphology of polymer assemblies. It was found that increasing the amount of star-like macro-RAFT agent facilitated the formation of higher-order morphologies. Additionally, effects of other reaction parameters including the length/number of the arm of the star-like macro-RAFT agent, degree of polymer (DP), monomer concentration on the morphology of star/linear block copolymer assemblies were also investigated. We expect that this work will offer new possibilities for the scalable preparation of polymer assemblies with unique structures and functions.

A wide variety of linear aryl esters can be obtained in generally good yields and high regioselectivities from alkyl terminal olefins via hydroesterification with aryl formates. The reaction process is operationally simple and requires no handling of toxic CO or strong acid.

Comprehensive Summary

A Pd-catalyzed regioselective hydroesterification of alkyl terminal olefins with aryl formates is described. A wide variety of linear carboxylic esters bearing various functional groups can be obtained in good yields with high regioselectivities under mild reaction conditions by using 1,2-DTBPMB or (p-F-Ph)₃P as ligand. The reaction process is operationally simple and requires no handling of toxic CO or strong acid. The resulting aryl esters can be readily converted to other carboxylic acid derivatives.

Surface topological glycosylation enhances mucoadhesion of bacteria.

Comprehensive Summary

Sugar moieties present on bacterial surface serve as pivotal regulators of bacterial activity. Precisely adjusting the abundance and distribution of surface sugar moieties can offer an important approach to manipulating bacterial behavior, but has been proven to be difficult. Herein, surface topological glycosylation is reported to mediate the interaction of bacteria with mucous layer. Alkynes functionalized by sugar moieties with different branching are synthesized through iterative Michael addition and amide condensation reactions. By a copper-catalyzed azide-alkyne cycloaddition, the resulting compounds with different branching structures can be attached onto bacterial surface that is modified with azido groups. As a proof-of-concept study, a set of topologically glycosylated probiotics (TGPs) is prepared using linear, two-branched, and tetra-branched compounds, respectively. The interaction between mucin and TGPs was studied and the results demonstrate that, compared to unmodified bacteria, TGPs exhibit an enhanced adhesive capacity to mucin, which increases with the branching numbers. Similar binding trend is observed in ex vivo colonic mucus adhesion experiments and bacteria glycosylated with tetra-branched compounds display the highest binding efficiency. This work proposes a chemical method to tune the abundance and distribution of sugar moieties on bacteria, providing unique significant insights into the manipulation of bacterial behavior through surface modification.